Sterilant composition

ABSTRACT

A biocidal, aqueous composition for killing bacteria, spores, fungi, and viruses on nonabsorbent surfaces comprises at least one quaternary ammonium compound, at least one aliphatic dialdehyde having from two to six carbon atoms, and at least one aliphatic hydroxyl compound having form one to eight carbon atoms. 
     This sterilant is stable for weeks, is especially useful between pH 4 to 9, and may additionally comprise a chelating agent.

RELATED U.S. APPLICATIONS

This is a continuation of application Ser. No. 07/866,010, filed Apr. 9,1992, now abandoned, which is a continuation of application Ser. No.758,400, filed Aug. 27, 1991, which has matured into U.S. Pat. No.5,124,359, granted Jun. 23, 1992, which is a continuation-in-part ofSer. No. 210,626 filed Jun. 23, 1988 which has matured into U.S. Pat.No. 4,923,899, granted May 8, 1992 which is a continuation-in-part ofSer. No. 139,166 filed Dec. 22, 1987 now abandoned which is acontinuation of Ser. No. 906,557 filed Sept. 8, 1986, now abandonedwhich is a continuation of Ser. No. 776,479 filed Sept. 16, 1985, nowabandoned which is a continuation-in-part of Ser. No. 692,776 filed Jan.18, 1985 now abandoned.

FIELD OF THE INVENTION

This invention relates to a broad-spectrum biocidal compositioneffective for the rapid killing of a wide variety of bacteria, spores,fungi, and viruses on a wide variety of nonabsorbent surfaces such asmetals, plastics, resins, woods, rubbers, ceramics, and glasses. Thecomposition of the present invention kills so many organisms on such awide variety of surfaces that it may be termed a sterilant.

Some of the articles which may be sterilized by the composition of thepresent invention are counters, floors, sheets, catheters, dialysismachine tubing, anesthetic breathing bags, surgical instruments, dentalbite blocks, saliva-draining tubes, respirator equipment, andenvironmental surfaces in general.

BACKGROUND OF THE INVENTION

In the past in medical and dental circles, steam sterilization ortreatment with ethylene oxide in a closed apparatus have been consideredideal ways of sterilizing equipment. But for many types or parts ofapparatus, steam sterilization is impractical because of the size ornumber of items to be sterilized. For parts of equipment which actuallycome in contact with the patient, such as dental bite blocks, anestheticbreathing bags, respirators, etc. it is impermissible for ethylene oxideto be used because residual trace amounts might harm the patient.

Hence, a stable, benign, broad-spectrum sterilant effective at a widerange of pH's is greatly desired by the medical/dental profession forenvironmental use, especially on nonabsorbent surfaces.

A disinfectant is generally considered to be an agent which destroysbacterial organisms which are growing, but not bacterial spores.Germicide and bactericide are approximately synonymous withdisinfectant. An antiseptic inhibits the growth of microorganisms. Asporicide kills spores of fungi molds, and bacteria. Since spores aremore resistant than bacteria, sporicides are generally consideredsterilizing agents. Biocides kill all living microorganisms, hence alsoare sterilizing agents. A virucide kills viruses; a fungicide killsfungi. The novel sterilant of this invention kills bacteria, spores,fungi and viruses. Hence, it may be termed a biocide or a sterilant.

The Hamilton U.S. Pat. No. 3,208,936, discloses combining a broad rangeof quaternary amines as germicides and foaming agents in recirculationtype toilets.

The Halley U.S. Pat. No. 3,785,971, is directed to a waste treatmentmaterial for a storage holding tank in which paraformaldehyde and analkali carbonate or hydroxide are combined.

U.S. Pat. No. 2,998,390, granted Aug. 29, 1961 to Hamilton and U.S. Pat.No. 3,107,216, granted Oct. 15, 1963 to Hamilton, disclose arecirculating toilet fluid which contains a quaternary ammonium salt.

"Quaternary Ammonium Salts as Germicidals. Nonacylated QuaternaryAmmonium Salts Derived from Aliphatic Amines," Shelton, R. S. et al.,Journal of the American Chemical Society, vol. 68, pp. 753-55 (1946),reported that alkyl quaternary ammonium salts have germicidal powers andN-benzyl substitutes do not affect this germical activity.

It was reported in Gardner, J. Disinfection, Sterilization &Preservation, p. 900, S. S. Block, ed., Lea & Febiger, 2nd ed. (1977) toinclude chelating agents with phenols and certain quaternary ammoniumsalts for enhanced activity against Gram-negative bacteria.

The Schattner U.S. Pat. No. 4,103,001 discloses an aqueous mixture ofphenol, sodium tetraborate, and sodium phenate solution to which isadded aqueous glutaraldehyde in order to kill some bacteria andbacterial spores. This mixture cannot be used against fungi or viruses.

The Stonehill U.S. Pat. No. 3,282,775 discloses a mixture of dialdehydesand a cationic surface active agent, plus a lower alcohol, which killsfour spore-forming bacteria, but not fungi or viruses.

The Pepper U.S. Pat. No. 3,016,328 discloses that simple dialdehydesplus a lower alkanol to the extent of about 60 to 70% and analkalinizing agent to yield a pH range of about 8 to 9.5 kill fourspore-forming bacteria, two of which are the same as in U.S. Pat. No.3,282,775.

Borick, et al in the Journal of Pharmaceutical Sciences, Vol. 53, No. 10at p. 1273 disclose that glutaraldehyde alkalinized with sodiumbicarbonate kills eight nonspore-forming bacteria, four spore-formingbacteria, one fungus, and nine viruses, but that this alkaline solutionwas stable only for about two weeks.

French Patent 2,321,300 discloses that a mixture of aldehyde andquaternary ammonium compound has antiseptic properties by reducing thegrowth of five bacteria of interest to the food industry.

British Patent 1,443,786 discloses that a mixture of glutaraldehyde, alower alcohol, and a highly ionizable salt at acidic pH ranges killsfour sporulating bacteria by ion-exchange with the calcium in the wallsof the bacterial spores.

The Wagner U.S. Pat. No. 4,107,312 discloses a disinfectant mixture of astrong formaldehyde solution, plus minor amounts of glyoxal andglutaraldehyde, plus a quaternary ammonium salt, methanol to stabilizethe formaldehyde, a nonionic wetting agent, optionally some alcohol orglycol, and a scent, all at a neutral pH in order to avoid corrosion ofaluminum toilets (or minimize corrosion of magnesium toilets) inaircraft.

The Mandt U.S. Pat. No. 4,444,785 discloses a disinfecting solution forsoft contact lenses against two nonsporulating bacteria comprising avery low concentration of 1,5 pentanedial at neutral pH compatible withthe human eye.

The Schaeufele U.S. Pat. No. 4,320,147 discloses a germicidalcomposition comprising quaternary ammonium chlorides, plus buildersalts, which are useful for disinfection against bacteria.

Canadian Patent No. 1,154,555 discloses a bactericide compositioncontaining formaldehyde, glutaraldehyde and a quaternary ammoniumingredient.

French Patent No. 2,145,444 discloses a bactericide compositioncontaining formaldehyde and a quaternary ammonium compound.

The Lockwood U.S. Pat. No. 3,505,690 relates to a disinfectantdispersing system.

The Buchalter U.S. Pat. No. 3,983,252 discloses a chemical disinfectingcomposition comprising a dialdehyde and an alkali metal salt of ahydrocarbon carboxylic acid and optionally an alcohol.

The Goldhaft U.S. Pat. No. 4,022,911 discloses a disinfectantcomposition comprising three essential active ingredients, namely adimethyl quaternary ammonium halide salt, a phenol or derivativethereof, and formaldehyde.

Oshchepkova and Kochkin in the Proceedings of the First All-UnionConference on Biocorrosion, Biodamage, and Marine Encrustation (1975),C.A.91:69799p report that a mixture of organotin fumarates oracryloyloxy stannate mixed with N-alkyl pyridinium salts ortetraalkylammonium salts protect wood samples in water from two commonbacteria-A. niger and P. purpureum.

OBJECTS OF THE INVENTION

It is an object of this invention to provide a stable, benign,nonodorous, solution which kills a broad-spectrum of bacteria, spores,fungi, and viruses rapidly at a wide range of pH.

It is a further object of this invention to provide a broadspectrumsterilant which will remain an active solution for at least severalweeks.

It is yet another object of this invention to provide a sterilant whichis effective on hard, nonabsorbent, "environmental" surfaces such asanesthetic breathing bags, dialysis tubing, respirators, dental biteblocks, saliva-draining tubes, and the like for which sterilization bysteam or ethylene oxide is either impractical or physiologicallydisfavored.

It is an object of the present invention to provide a sterilantcomposition effective for killing rapidly individual microorganisms or acombination of several different kinds of microorganisms, such asbacteria, spores, fungi and/or viruses.

Another object of the invention is to provide a sterilant for a widevariety of hard surfaces such as metals, plastics, resins, rubbers,ceramics, and glasses.

Yet another object of the present invention is to provide a sterilantwhich is effective in the presence of high concentrations of blood,sputum, feces, urine, vomitus, and other animal exudates.

Other objects of the present invention will be apparent to those skilledin the art.

SUMMARY OF THE INVENTION

Surprisingly, a broad-spectrum sterilant capable of rapidly killingbacteria, sporulating bacteria, spores, fungi, and viruses can beachieved by combining in an aqueous solution an effective amount of atleast one quaternary ammonium compound, at least one aliphaticdialdehyde having from two to six carbon atoms, and at least onealiphatic hydroxyl compound having from one to eight carbon atoms.

Another aspect of the invention relates to the use of the novelsterilant on "hard" or "environmental" surfaces (nonabsorbing) such asmedical or dental equipment for which previously steam sterilization ortreatment with ethylene oxide were employed.

The sterilant of the present invention relates to a liquid compositionwhich is effective for rapidly killing at least one microorganism or anycombination of two or more different microorganisms such as bacteria,spores, fungi and viruses.

For still another aspect of the invention, the novel sterilant isemployed over a wide range of pH and is stable for several weeks afterhaving been compounded.

Yet another aspect of the present invention arises from its efficacy inthe presence of high concentrations of blood, sputum, urine, feces,vomitus or other bodily liquids or suspensions.

A further aspect of the present invention is its efficacy in sterilizinghard surfaces of metals, plastics, rubbers, resins, wood, ceramics, orglasses.

A typical embodiment of the invention comprises:

    ______________________________________                                        Component               Weight %                                              ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Glutaraldehyde          2.6                                                   Isopropyl alcohol       0.2                                                   Propylene glycol         0.16                                                 Sodium nitrite           0.11                                                 Tetrasodium ethylenediamine tetraacetate                                                               0.015                                                Water                   balance                                               ______________________________________                                    

Processes for employing these sterilant compositions are also disclosedherein.

DETAILED DESCRIPTION OF THE INVENTION

As discussed above, the prior art discloses individual compounds ormixtures of compounds which kill or inhibit the growth of a narrow rangeof organisms such as some bacteria, spores, fungi, or viruses. Thesynergistic combination of the seven components of the present inventionunexpectedly kills all types of the names organisms, hence it is asterilant. Among the classes of organisms killed by the composition ofthe present invention alone or admixed together are Gram-negativebacteria, Gram-positive bacteria, algae, protozoa, Gram-positivespore-forming bacteria, fungi, and many types of viruses.

Among the many typos of viruses killed by the composition of the presentinvention are: orbiviruses, orthomyxoviruses, papovaviruses,paramyxoviruses, parvoviruses, picornaviruses, poxviruses,coronaviruses, flaviviruses, herpesviruses, adenoviruses, arenaviruses,bunyaviridae, caliciviruses, reoviruses, retioviruses, rhabdoviruses,rotaviruses, togaviruses, and various unclassified viruses, plus plantviruses.

In addition to the bacteria, spores, protozoa, algae, fungi, and virusescategorized above, the composition of the present invention can killalone or in combination with the other organisms typified above variousmiscellaneous organisms from the Chlamydia Coxiella, Ehrlichia,Rickettsia, Rochalimaea, Wolbachia, and Thai tick typhus.

It is to be emphasized that the composition of the present invention isa sterilant which can kill any or all of the types of organismsdescribed here alone or in any combination.

At the end of the Examples of this specification and before the claims,several hundred representative specific organisms are listed in Tables Ito VII on which the synergistic composition of the present invention iseffective.

The cationic, quaternary salts useful in the present invention maycontain either or both of aliphatic and aromatic moieties. Althoughquaternary ammonium salts are preferred, cationic phosphonium, orsulfonium, or any other positive nonmetallic nuclei may be selected.Some of the aliphatic or alicyclic substituents for the quaternary ionsare alkyl groups containing one to 30 carbon atoms both linear andbranched, alkoxy groups also containing one to 30 carbon atoms bothlinear and branched, alicyclic groups such as cyclohexyl and itsalkylated or alkyloxylated derivatives, and halogenated alkyl,halogenated alicyclic, or halogenated alkyloxy derivatives.

Aromatic moieties, which may themselves be substituted by aliphatic,alicyclic, alkyloxy groups, useful as substituents for the quaternarycationic salts of the present invention are benzyl, tolyl, xylyl,naphthyl, pyridyl, benzal, quinolyl and the like.

More specifically, some aliphatic quaternary ammonium salts which areuseful in the present invention are: tetramethyl ammonium halide,trimethylethyl ammonium halide, dimethyldiethyl ammonium halide,methyltriethyl ammonium halide, tetraethyl ammonium halide,cetyldimethylethyl ammonium halide, trimethyln-propyl ammonium halide,dimethyldin-propyl ammonium halide, methyltrin-propyl ammonium halide,tetran-propyl ammonium halide, methylethyln-propyln-butyl ammoniumhalide, ethyln-propyln-pentyl ammonium halide, trimethylallyl ammoniumhalide, dimethyldiallyl ammonium halide, methyltriallyl ammonium halide,tetraallyl ammonium halide, N,N,N,N',N',N'-hexaethyl-1,2-ethylenediammoniumhalide, N,N,N,N',N',N'-hexaethyl-1,4-butylene diammoniumhalide, N,N,N'-dibenzyl-N,N,N',N', tetramethyl-1,2-ethylene diammoniumhalide,N,N'-di(4-chlorobenzyl)-N,N,N',N'-tetramethyl-1,2-ethylenediammoniumhalide,N,N,N'-tetraethyl-N,n"-dioctadecyl-1,2-ethylene diammonium halide,N,N,N',N'-tetraethyl-N,N'-dihexadecyl-1,4-butylene diammonium halide,octadecyltrimethyl ammonium halide, dioctadecyldimethyl ammonium halide,trioctadecylmethyl ammonium halide tetraoctadecyl ammonium halide,hexadecyltriethyl ammonium halide, hexadecyldimethylethyl ammoniumhalide, hexadecyldiethylmethyl ammonium halide, didecyldioctyl ammoniumhalide, didecyldihexyl ammonium halide, and hexyloctyldecyldodecylammonium halide.

Some representative useful quaternary ammonium salts containing anaromatic moiety include:

benzylodecyldimethyl ammonium halide, o-tolyldodecyldimethyl ammoniumhalide, m-tolyldodecyldimethyl ammonium halide,

p-tolyldodecyldimethyl ammonium halide, 2,3-xylyldodecyldimethylammonium halide, 2,4-xylydodecyldimethyl ammonium halide,2,5-xylyldodecyldimethyl ammonium halide, 3,4-xylyldodecyldimethylammonium halide, 3,5-xylyldodecyldimethyl ammonium halide,

2-chlorobenzyldodecyldimethyl ammonium halide,

3-chlorobenzyldodecyldimethyl ammonium halide,

4-chlorobenzyldodecyldimethyl ammonium halide,

2,3-dichlorobenzyldodecyldimethyl ammonium halide,

2,4-dichlorobenzyldodecyldimethyl ammonium halide,

2,5-dichlorobenzyldodecyldimethyl ammonium halide,

2,6-dichlorobenzyldodecyldimethyl ammonium halide,

3,4-dichlorobenzyldodecyldimethyl ammonium halide,

3,5-dichlorobenzyldodecyldimethyl ammonium halide,

2-nitrobenzyldodecyldimethyl ammonium halide,

3-nitrobenzyldodecyldimethyl ammonium halide,

4-nitrobenzyldodecyldimethyl ammonium halide,

2,4-dinitrobenzyldodecyldimethyl ammonium halide,

3,5-dinitrobenzyldodecyldimethyl ammonium halide,

2-sulfobenzyldodecyldimethyl ammonium halide,

3-sulfobenzyldodecyldimethyl ammonium halide,

4-sulfobenzyldodecyldimethyl ammonium halide,

2-carboxybenzyldodecyldimethyl ammonium halide,

3-carboxybenzyldodecyldimethyl ammonium halide,

4-carboxybenzyldodecyldimethyl ammonium halide, benzylhexyldimethylammonium halide, benzyloctyldimethyl ammonium halide,benzyldecyldimethyl ammonium halide, benzyldodecyldimethyl ammoniumhalide, benzyltetradecyldimethyl ammonium halide,benzylhexadecyldimethyl ammonium halide, benzyloctadecyldimethylammonium halide.

Some representative, useful quaternary ammonium salts containingheterocyclic, aromatic moieties include:

n-hexylpyridinium halide, n-octylpyridinium halide,

n-decylpyridinium halide, n-dodecylpyridinium halide,

n-tetradecylpyridinium halide, n-hexadecylpyridinium halide,

n-hexyllutidinium halide, n-octyllutidinium halide,

n-decyllutidinium halide, n-dodecyllutidinium halide,

n-tetradecyllutidinium halide, n-hexadecyllutidinium halide,

n-hexylpicolinium halide, n-octylpicolinium halide,

n-decylpicolinium halide, n-dodecylpicolinium halide,

n-tetradecylpicolinium halide, n-hexadecylpicolinium halide,

n-hexylquinolinium halide, n-octylquinolinium halide,

n-decylquinolinium halide, n-dodecylquinolinium halide,

n-tetradecylquinolinium halide, n-hexadecylquinolinium halide,

n-hexylisoquinolinium halide, n-octylisoquinolinium halide,

n-decylisoquinolinium halide, n-dodecylisoquinolinium halide,

n-tetradecylisoquinolinium halide, n-hexadecylisoquinolinium

halide, n-hexylquinazolinium halide, n-octylquinazolinium halide,

n-decylquinazolinium halide, n-dodecylquinazolinium halide,

n-tetradecylquinazolinium halide, n-hexadecylquinazolinium halide,

n-hexylquinoxalinium halide, n-octylquinoxalinium halide,

n-decylquinoxalinium halide, n-dodecylquinoxalinium halide,

n-tetradecylquinoxalinium halide, n-hexadecylquinoxalinium halide,

n-hexylpyridopyridinium halide, n-octylpyridopyridinium halide,

n-decylpyridopyridinium halide, n-dodecylpyridopyridinium halide,

n-tetradecylpyridopyridinium halide, and

n-hexadecylpyridopyridinium halide.

The preferred counter ions for the quaternary cationic salts arehalides, especially chloride and bromide. Particularly useful forpracticing the present invention are alkylbenzyldimethyl ammoniumchlorides, wherein the alkyl groups contain between 10 and 18 carbonatoms, and cetyldimethylethyl ammonium bromide. The useful range ofquaternary cationic salts in an effective amount of sterilant is fromabout 0.05% to 3% in actual use by weight.

Other counter ions, anions, useful in the practice of the presentinvention to neutralize the positive charge of the ammonium,phosphonium, sulfonium, or other positive moieties can be found in thefollowing list bicarbonate, bisulfite, fluoride, borate, carbonate,nitrite, nitrate, phosphite, phosphate, sulfite, sulfate, chloride,hypochlorite, chlorite, chlorate, perchlorate, hydroxide, fluoborate,iodide, iodate, periodate, and bromate.

The solubility of the various solutes in the novel sterilant of theinstant invention is improved by using small amounts of alkanols havingfrom one to six carbon atoms and/or glycols having from two to fourcarbon atoms. These alkanols and glycols also have concomitant andperipheral biocidal effect. Especially useful alkanols are methanol,ethanol, and isopropyl alcohol. Especially useful polyols are glycolssuch as ethylene glycol, propylene glycol, diethylene glycol, as well asglycerine. In the diluted solution for actual use, the effective amountfor the alkanol is from about 0.1% to 3% by weight, and the effectiveamount for the polyol or glycol is from about 0.1% to 3% by weight.

Other alcohols having eight or less carbon atoms useful in the practiceof the present invention are:

1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol,2-methyl-2-butanol, 2-methyl-3-butanol, 2-methyl-4-butanol,2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol,2,2-dimethyl-3-butanol, 2,2-dimethyl-4-butanol, 2,3-dimethyl-2-butanol,2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,2-methyl-4-pentanol, 2-methyl-5-pentanol, 3-methyl-1-pentanol,3-methyl-2-pentanol, 3-methyl-3-pentanol, 2,2-diethyl-1-ethanol,1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol,2,2,3-trimethyl-3-butanol, 2,3-dimethyl-3-pentanol,2,4-dimethyl-3-pentanol, 3-ethyl-1-pentanol, 3-ethyl-2-pentanol,3-ethyl-3-pentanol, 4-ethyl-1-pentanol, 4-ethyl-2-pentanol,4-ethyl-3-pentanol, 2-ethyl-1-pentanol, 2-methyl-1-hexanol,2-methyl-2-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol,3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol,3-methyl-2-hexanol, 4-methyl-2-hexanol, 3-methyl-3-hexanol,3-methyl-4-hexanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol,2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol,5-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol,2-methyl-2-heptanol, 3-methyl-2-heptanol, 4-methyl-2-heptanol,5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol,3-methyl-3-heptanol, 4-methyl-3-heptanol, 5-methyl-3-heptanol,6-methyl-3-heptanol, 2-methyl-4-heptanol, 3-methyl-4-heptanol,4-methyl-4-heptanol, 5-methyl-4-heptanol, 6-methyl-4-heptanol,2,2-dimethyl-1-hexanol, 3,3-dimethyl-1-hexanol, 4,4-dimethyl-1-hexanol,5,5 -dimethyl-1-hexanol, 2,3-dimethyl-1-hexanol, 2,4-dimethyl-1-hexanol,2,5-dimethyl-1-hexanol, 3,4-dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol,2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, and5-ethyl-1-hexanol.

Other glycols having eight or less carbon atoms useful in the practiceof the present invention are:

1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,2-methyl-1,2-propanediol, 2,methyl-1,3-propanediol, 1,2-pentanediol,1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol,2-methyl-1,2-butanediol, 2-methyl-1,3-butanediol,2-methyl-1,4-butanediol, 2-methyl-2,3-butanediol,2-methyl-3,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol,1,5-hexanediol, 1,6-hexanediol, 2-methyl-1,2-pentanediol,2-methyl-1,3-pentanediol, 2-methyl-1,4-pentanediol,2-methyl-1,5-pentanediol, 2-methyl-2,3-pentanediol,2-methyl-2,3-pentanediol, 2-methyl-2,4-pentanediol,2-methyl-2,5-pentanediol, 2-methyl-3,4-pentanediol,2-methyl-3,5-pentanediol, 2-methyl-4,5-pentanediol,2,3-dimethyl-1,2-butanediol, 2,3-dimethyl-1,3-butanediol,2,3-dimethyl-1,4-butanediol, 2,3-dimethyl-2,3-butanediol.

Certain salts with anions at less than full oxidation state, such asnitrite, bisulfite, or chlorite, may be optionally employed in the novelsterilant solution of the instant invention to prevent corrosion, aswell as for their biocidal activity.

Also useful in the practice of the present invention are cations whereinthe metal oxidation state is lower than its chemically possible maximum.

Some useful compounds with less than full oxidation states are found inthe following salts first some with reduced anions and then some saltswith less oxidized cations, as follows: sodium phosphite, sodiumsulfite, sodium hypochlorite, sodium chlorite, sodium chlorate, sodiumselenite, sodium arsenite, sodium hypobromite, sodium bromite, sodiumbromate, sodium stannite, sodium antimonite, sodium tellurite, sodiumferrocyanide, sodium manganite, sodium manganate, potassium phosphite,potassium, sulfite, potassium hypochorite, potassium chlorite, potassiumchlorate, potassium selenite, potassium arsenite, potassium hypobromite,potassium bromite, potassium bromate, potassium stannite, potassiumantimonite, potassium tellurite, potassium ferrocyanide, potassiummanganite, potassium manganate, lithium phosphite, lithium sulfite,lithium hypochlorite, lithium chlorite, lithium chlorate, lithiumselenite, lithium arsenite, lithium hypobromite, lithium bromite,lithium bromate, lithium stannite, lithium antimonite, lithiumantimonite, lithium tellurite, lithium ferrocyanide, lithium manganite,lithium manganate, rubidium nitrite, rubidium phosphate, rubidiumsulfite, rubidium hypochlorite, rubidium chlorite, rubidium chlorate,rubidium selenite, rubidium arsenite, rubidium hypobromite, rubidiumbromite, rubidium bromate, rubidium stannite, rubidium antimonite,rubidium tellurite, rubidium ferrocyanide, rubidium manganite, rubidiummanganate, cesium nitrite, cesium phosphite, cesium sulfite, cesiumhypochlorite, cesium chlorite, cesium chlorate, cesium selenite, cesiumarsenite, cesium hypobromite, cesium bromite, cesium bromate, cesiumstannite, cesium antimonite, cesium telurite, cessium ferrocyanide,cesium manganite, cesium manganate, ferrous ferrocyanide, ferrousferricyanide, cuprous chloride, ferrous phosphate, stannous chloride,ferrous sulfate, manganous sulfate, plumbous sulfate, and chromouschloride.

Particularly useful are sodium, potassium, lithium, and ammonium saltsof nitrite, bisulfite, and chlorite; especially useful is sodiumnitrite. These optional salts may be employed in the range from 0.05% toabout 2.0% by weight of the actual solution employed.

A chelating agent may be optionally employed in the broad-spectrumsterilant of the present invention from 0% to 0.025% by weight to aid insolubility of the other components, to counteract any deleteriouseffects from diluting concentrated commercial strengths with hard waterfor use, and to help break down the coatings of spores, which have ahigh concentration of multivalent ions. The preferred chelating agent topractice the current invention may range from 0% to 0.025% by weight andis ethylene diamine tetraacetic acid (EDTA). Partial esters or salts ofEDTA may also be used. An example of a salt of EDTA is tetrasodiumethylenediamine tetraacetate.

Other useful chelating agents may be found in the following acids, fullsalts, or partial salts of: oxalic acid, malonic acid, oxaldihydrixamicacid, diaminoglyoxime, dithiomalonic acid, glyoxime, maleic acid,fumaric acid, oxalacetic acid, diglycolic acid, tartaric acid,oxalenediuramidoxime, thiodiglycolic acid, iminodiacetic acid,nitrilotriacetic acid, dimethylglyoxime, hydrazine-N,N'-diacetic acid,citraconic acid, itaconic acid, 2,4-pentanedione, glutaric acid,N-methyliminodiacetic acid, glutamic acid, aconitric acid (trans),gluconic acid, 1,2-cyclohexanediamine-N,N,N'-tetraacetic acid(cis&trans), 1,2-ethylenediamine-N,N,N',N'-tetraacetic acid,N'-benzylethylenediamine-N,N,N'-triacetic acid,diethylenetriamine-N,N,N',N",N"-pentaacetic acid,hexamethyldiamine-N,N,N',N'-tetraacetic acid,2,2"-ethylenedioxybis(ethyliminodiacetic acid), 2,2'-oxybis(propyliminodiacetic acid), triethylenetetraminehexaacetic acid,1,3,5-triaminocyclohexanehexaacetic acid, and ethyl acetoacetate.

A dialdehyde containing up to six carbon atoms is a component of thebroad-spectrum sterilant of the present invention. Dialdehydes includemalonaldehyde, succinaldehyde, oxaldehyde (glyoxal), adipaldehyde, andpreferably glutaraldehyde. Alternatively, these compounds may be termedaliphatic dials, e.g. 1,5 pentanedial. By themselves, these compoundsare effective germicides to some degree, at high pH, but they fail tohave the wide breadth and speed of killing of the mixture of the currentinvention. This is especially true for the killing of the sporulentbacteria, where the dialdehydes alone can take up to ten hours to killspores, and for many viruses, where dialdehydes are ineffective. In thefinal dilution as used, in the present invention, an effective amount ofthe dialdehyde is from about 0.5% to about 7% by weight. A concentrationof dialdehyde of about 2.6 to 5 weight % is preferred and aconcentration of dialdehyde of 3.2 weight % is especially preferred.

Some useful dialdehydes in the practice of the present invention are thefollowing compounds and their mixtures: 1,2-ethanedial, 1,3-propanedial,1,4-butanedial, 1,5-pentanedial, 2-methyl-1,4-butanedial,2-methyl-1,3-propanedial, 2,2-dimethyl-1,3-propanedial,2,3-dimethyl-1,4-butanedial, 2,2-dimethyl-1,4-butanedial, 1,6hexanedial, 2-methyl-1,5-pentanedial, 3-methyl-1,5-pentanedial,2-ethyl-1,3-propanedial and 2-n-propyl-1,3-propanedial. Some examples ofheterocyclic dialdehydes are furan-2,5-dialdehyde, furan-3,4-dialdehyde,thiophene-2,5-dialdehyde, thiophene-3,4-dialdehyde,pyrrole-2,5-dialdehyde, pyrrole-3,4-dialdehyde,imidazole-4,5-dialdehyde, pyrazole-3,4-dialdehyde,1,2,3-triazole-4,5-dialdehyde, pyrazine-2,3-dialdehyde,pyrimidine-4,5-dialdehyde, pyridazine-3,4-dialdehyde,pyridazine-4,5-dialdehyde. Aliphatic dialdehydes are preferred, butheterocyclic dialdehydes such as those named above may also be employed.

As a practical matter, it is preferred to produce the broad-spectrumsterilant of the present invention in the form of one or moreconcentrated solutions prior to transport and storage. Theconcentrations of these solutions would be 50 to 100-fold higherstrength than the actual use-strengths given above. After transport andstorage, the user, normally a medical or dental technician, will dilutethe concentrate to produce an effective amount at the ultimate dilutionand then add the dialdehyde.

In concentrated form, a preferred embodiment of the sterilantconcentrate of the present invention would have the followingapproximate concentrations by weight:

    ______________________________________                                                               Weight %                                               ______________________________________                                        Alkyl*benzyldimethylammonium chloride                                                                  7                                                    *50% C-12, 30% C-14, 17% C-16, 3% C-18                                        Cetyldimethylethylammonium bromide                                                                     7                                                    Isopropyl alcohol        14                                                   Propylene glycol         12                                                   Sodium nitrite           7                                                    EDTA                     1.5                                                  Water, balance up to 100%                                                     ______________________________________                                    

In actual practice, the user will have prepared a desired quantity ofthe diluted sterilant concentrate by diluting the sterilant concentratewith distilled or tap water. This resulting solution will serve,further, as the diluent for the dialdehyde concentrate then to be addedthereto.

The diluted sterilant solution after combination is an exceptionallybroad-spectrum sterilant on a wide variety of metal, plastic,cross-linked resin, rubber, composite, coated, painted or natural wood,ceramic, or glass non-adsorbent surfaces, exemplified by but not limitedto the following: stainless steels (various), steels, not stainless(various), galvanized iron, copper, brass, aluminum, chromium platedmetals, tinned plating metals, enameled metals, polyethylene,polypropylene, polystyrene, acrylics, polyacetals, nylons, "epoxyresin"-coated wood, polyurethane-coated wood, alkyd resin painted wood,alkyd resin-coated metal, oil-based painted wood, phenolformaldehyderesin laminates ("Formica" type), polyvinyl chloride-based furnituresurfaces ("Naugahyde" type), gum rubber surgical/dental adjuncts (dentaldam, tubing, catheters, gloves), hard rubber devices (bite blocks),water-based, latex-painted wood, glazed porcelain and other ceramics andvarious types of glass such as lime, flint, and borosilicates.

The present invention will now be described by reference to thefollowing examples, which are not to be deemed limitative of the presentinvention in any manner thereof.

EXAMPLE A

This example illustrates the preparation of an effective sterilizingamount of a final user solution of the sterilant composition of theinvention.

A 15 ml ampule of the above sterilant concentrate was diluted withdistiled water to a final volume of 1 liter. This was a dilution ratioof about 66.7:1. To this solution was added 50 ml of an aqueous 50% byweight solution of glutaraldehyde concentrate. On a weight basis, theconcentration of glutaraldehyde will be about 2.6% in the final usersolution.

Thus in the final user solution, the concentrations of the variouscomponents in the diluted sterilant will be as follows:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Isopropyl alcohol       0.2                                                   Propylene glycol         0.16                                                 Sodium nitrite          0.1                                                   EDTA                     0.02                                                 Dialdehyde, esp. glutaraldehyde                                                                       2.6                                                   Water                   balance                                               ______________________________________                                    

The diluted sterilant composition of the present invention may beemployed over a wide, useful pH range from about pH 4 to about pH 9. Thepreferred range for use is from about pH 5 to about pH 8. This is inmarked contrast to the use of alkalinized dialdehydes alone, which areeffective only from about pH 7 to about pH 8.5. Although buffers mayoptionally be employed to keep the sterilant of the instant inventionwithin a narrow pH range, no buffer is necessary to practice thisinvention.

EXAMPLE B

This example illustrates the preparation of an effective sterilizingamount of a final user solution of the sterilant composition of theinvention.

A 15 ml ampule of the above sterilant concentrate was diluted withdistilled water to a final volume of 750 ml. This was a dilution ratioof about 50:1. To this solution was added 50 ml of an aqueous 50% byweight solution of glutaraldehyde concentrate. On a weight basis, theconcentration of glutaraldehyde will be about 3.2% in the final usersolution.

Thus, in the final user solution, the concentrations of the variouscomponents in the diluted sterilant will be as follows:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.15                                                  Cetyldimethylethylammonium bromide                                                                    0.15                                                  Isopropyl alcohol       0.25                                                  Propylene glycol        0.20                                                  Sodium nitrite          0.15                                                  EDTA                     0.025                                                Dialdehyde, esp. glutaraldehyde                                                                       3.2                                                   Water                   balance                                               ______________________________________                                    

The diluted sterilant composition of the present invention may beemployed over a wide, useful pH range from about pH 4 to about pH 9. Thepreferred range for use is from about pH 5 to about pH 8. This is inmarked contrast to the use of alkalinized dialdehydes alone, which areeffective only from about pH 7 to about pH 8.5. Although buffers mayoptionally be employed to keep the sterilant of the instant inventionwithin a narrow pH range, no buffer is necessary to practice thisinvention.

EXAMPLE 1

This example illustrates the effectiveness of the sterilant compositionof EXAMPLE A for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppmhard water as the diluent for test purposes:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Isopropyl alcohol       0.2                                                   Propylene glycol        0.16                                                  Sodium nitrite          0.11                                                  EDTA                    0.02                                                  Glutaraldehyde          2.60                                                  Water                   balance                                               ______________________________________                                    

Employing the Use-Dilution Method of the Association of OfficialAgricultural Chemists (AOAC) 60 ring carriers were tested on threebatchs each for efficacy against the following organisms (US EPAProcedure DIS/TSS-1 and 2 of January 1982); Salmonella chloeraesius ATCC10708 (Gram-negative), Staphylococcus aureus ATCC 6538 (Gram-positive),and Pseudomonas aeruginosa ATCC 15442 (Gram-positive, nosocomialpathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 2

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659and Clostridium sporogenes ATCC 3584 employing US EPA ProcedureDIS/TSS-9 of April 1981 (AOAC Sporicidal Test). Sixty carriers for eachtype of surface, porcelain penicylinders and silk suture loops, for eachof three samples for each of three batches involved a total of 720carriers.

As required, all microorganisms were killed on all carriers in about 5hours, less than 6 hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard onlyafter 10 hours of contact.

EXAMPLE 3

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst pathogenic fungus Trichophyton mentagrophytes ATCC 27289according to the AOAC Fungicidal Test by EPA procedure DIS/TSS-6 ofAugust 1981. For this fungus two batches were used for two samples eachkilling all organisms within 10 minutes at 20 degrees C.

EXAMPLE 4

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention in killing viruses, some of which none of thecomponents of the novel sterilant can kill individually under the sameconditions.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst the following viruses: Herpes Simplex I and II, Coxsackie virusB1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virusII, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, allaccording to EPA procedure DIS/TSSD-7. For two batches each, fourreplicates were carried by ten-fold dilution and measured to three-logdiminution. After incubation, the samples were recovered afteradsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20degrees C. It is known that alkalinized glutaraldehyde fails toinactivate at least Coxsackie virus and Poliovirus I under theseconditions.

EXAMPLE 5

This example illustrates the effectiveness of the sterilant compositionof EXAMPLE B for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppmhard water as the diluent for test purposes:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.15                                                  Cetyldimethylethylammonium bromide                                                                    0.15                                                  Isopropyl alcohol       0.25                                                  Propylene glycol        0.20                                                  Sodium nitrite          0.15                                                  EDTA                     0.025                                                Glutaraldehyde          3.2                                                   Water                   balance                                               ______________________________________                                    

Employing the Use-Dilution Method of the Association of OfficialAgricultural Chemists (AOAC) 60 ring carriers were tested on threebatchs each for efficacy against the following organisms (US EPAProcedure DIS/TSS-1 and 2 of January 1982); Salmonella choleraesius ATCC10708 (Gram-negative), Staphylococcus aureus ATCC 6538 (Gram-positive),and Pseudomonas aeruginosa ATCC 15442 (Gram-positive, nosocomialpathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 6

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659and Clostridium sporogenes ATCC 3584 employing US EPA ProcedureDIS/TSS-9 of April 1981 (AOAC Sporicidal Test). Sixty carriers for eachtype of surface, porcelain penicylinders and silk suture loops, for eachof three samples for each of three batches involved a total of 720carriers.

As required, all microorganisms were killed on all carriers in about 5hours, less than 6 hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard onlyafter 10 hours of contact.

EXAMPLE 7

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst pathogenic fungus Trichophyton mentagrophytes ATCC 27289according to the AOAC Fungicidal Test by EPA procedure DIS/TSS-6 ofAugust 1981. For this fungus two batches were used for two samples eachkilling all organisms within 10 minutes at 20 degrees C.

EXAMPLE 8

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention in killing viruses, some of which none of thecomponents of the novel sterilant can kill individually under the sameconditions.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst the following viruses: Herpes Simplex I and II, Coxsackie virusB1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virusII, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, allaccording to EPA procedure DIS/TSSD-7. For two batches each, fourreplicates were carried by ten-fold dilution and measured to three-logdiminution. After incubation, the samples were recovered afteradsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20degrees C. It is known that alkalinized glutaraldehyde fails toinactivate at least Coxsackie virus and Poliovirus I under theseconditions.

The sterilant composition of the present invention has the advantages ofbeing effective to kill a broad spectrum of microorganisms very rapidlywith low concentrations of the active ingredients. The sterilantcomposition as a combination of ingredients is more effective againstseveral microorganisms together at the same time than would be possibleby using each active ingredient separately against the combination ofmicroorganisms.

The sterilants of the disclosure above exemplified by the preferredembodiments of the various Examples are effective against a wide varietyof microorganisms such as those of Tables I through VII.

                  TABLE I                                                         ______________________________________                                        VIRUSES                                                                       ______________________________________                                        ADENOVIRUSES                                                                  Avian adenovirus Types 1-10                                                   Marble spleen disease virus                                                   Bovine adenovirus Types 1-8                                                   Canine adenovirus                                                             Infectious canine hepatitis                                                   Human adenovirus Types 1-41                                                   Mouse adenovirus                                                              Swine adenovirus                                                              Baboon adenovirus                                                             Chimpanzee adenovirus                                                         Simian adenovirus Types 1-39                                                  ARENAVIRUSES                                                                  Amapari                                                                       Junin                                                                         Latino                                                                        Lymphocytic choriomeningitis                                                  Bolivian Hemorrhagic Fever                                                    Parana                                                                        Pichinde virus                                                                Tacaribe virus                                                                Tamiami virus                                                                 BUNYAVIRIDAE                                                                  Anopheles Group                                                               Bunyamwera Super Group                                                        Bwamba Group                                                                  California Group                                                              Capim Group                                                                   Gamboa Group                                                                  Guama Group                                                                   Koongol Group                                                                 Patois Group                                                                  Simbu Group                                                                   Tete Group                                                                    Turlock Group                                                                 Phleboviruses                                                                 Nairoviruses                                                                  Hantaviruses                                                                  CALICIVIRUSES                                                                 Feline conjunctivitis                                                         Feline picornavirus                                                           Feline stomatitis                                                             CORONAVIRUSES                                                                 Calf diarrheal coronavirus                                                    Canine coronavirus                                                            Feline infectious peritonitis                                                 Hemagglutinating encephalomyelitis                                            Human coronavirus                                                             Infectious bronchitis                                                         Mouse hepatitis virus                                                         Rabbit coronavirus                                                            Rat coronavirus                                                               Sialodacryoadenitis virus                                                     Transmissible gastroenteritis                                                 Turkey enteritis coronavirus                                                  FLAVIVIRUSES                                                                  Banzi                                                                         Bukalasa                                                                      Bussuquara                                                                    Cowbone ridge                                                                 Dakar bat                                                                     Dengue Types 1-4                                                              Edge Hill                                                                     Entebbe bat                                                                   Ilheus                                                                        Japanese encephalitis                                                         Kokobera                                                                      Kyasanur                                                                      Louping III                                                                   Modoc                                                                         Montana myotis leukoencephalitis                                              Murray Valley encephalitis                                                    Ntaya                                                                         Powassan                                                                      Rio Bravo                                                                     Russian spring-summer encephalitis                                            Sepik                                                                         Simian hemorrhagic fever                                                      St. Louis encephalitis                                                        Stratford                                                                     Tenbusu                                                                       Uganda S                                                                      West Nile                                                                     Yellow fever                                                                  Zika                                                                          HERPESVIRUSES                                                                 Avian laryngotracheitis                                                       Duck enteritis                                                                Falcon herpesvirus                                                            Lake Victoria cormorant                                                       Marek's disease                                                               Parrot herpesvirus                                                            Pigeon herpesvirus                                                            Turkey herpesvirus                                                            Bovine herpesvirus                                                            Infectious bovine rhinotracheitis                                             Canine herpesvirus                                                            Equine cytomegalovirus                                                        Equine herpesvirus                                                            Feline herpesvirus                                                            Feline rhinotracheitis virus                                                  Channel catfish                                                               Herpesvirus salmonis                                                          Guinea pig herpes-like virus                                                  Guinea pig salivary gland virus                                               Guinea pig X virus                                                            Burkitt's lymphoma                                                            Cytomegalovirus                                                               Herpes simplex Types 1 & 2                                                    Varicella                                                                     Varicella-Zoster                                                              B Virus                                                                       Hepatitis A, B & C virus                                                      Herpesvirus aotus                                                             Herpesvirus ateles                                                            Herpesvirus saguinus                                                          Herpesvirus saimiri                                                           Monkey cytomegalovirus                                                        Simian herpesvirus 2 & 3                                                      Squirrel monkey cytomegalovirus                                               Pseudorabies                                                                  Caprine herpesvirus                                                           Frog Virus 4                                                                  Mouse Salivary Gland Virus                                                    Rabbit herpesvirus                                                            ORBIVIRUSES                                                                   Bluetongue all types                                                          Changuinola                                                                   Colorado tick fever                                                           Corriparta                                                                    Epizootic hemorrhagic disease of deer                                         Ieri                                                                          Irituia                                                                       Lebombo                                                                       Tribec                                                                        Wad Medani                                                                    ORTHOMYXOVIRUSES                                                              Avian Influenza                                                               Horse Influenza A                                                             Human Influenza A, B & C                                                      Swine Influenza                                                               Thogoto                                                                       PAPOVAVIRUSES                                                                 Human polyoma                                                                 Bovine papilloma                                                              Human papilloma                                                               JC virus                                                                      K-virus                                                                       Lymphotropic Papovavirus                                                      Papilloma                                                                     Polyoma                                                                       Simian Papovavirus                                                            SV-40                                                                         PARAMYXOVIRUSES                                                               Bluegill                                                                      Bovine morbillivirus-like                                                     Bovine respiratory syncytial virus                                            Canine distemper                                                              Canine parainfluenza                                                          Fer de Lance virus                                                            Measles                                                                       Mumps                                                                         Nariva                                                                        Newcastle disease                                                             Parainfluenza                                                                 Pneumonia virus of mice                                                       Respiratory syncytial                                                         Simian paramyxovirus                                                          Subacute sclerosing panencephalitis                                           Yucaipa                                                                       PARVOVIRUSES                                                                  Adeno-associated virus                                                        Aleutian disease                                                              Avian adeno-associated                                                        Bovine parvovirus                                                             Canine parvovirus                                                             Feline panleukopenia                                                          Hemorrhagic encephalopathy                                                    Porcine parvovirus                                                            PICORNAVIRUSES                                                                Poliovirus 1, 2 & 3                                                           Coxsackievirus, all types                                                     Echovirus, all types                                                          Enterovirus, all types                                                        Human rhinovirus, all types                                                   Avian encephalomyelitis                                                       Baboon enterovirus                                                            Bovine enterovirus, all types                                                 Bovine rhinovirus, all types                                                  Encephalomyocarditis                                                          Mouse encephalomyelitis                                                       Porcine enterovirus, all types                                                Rat encephalomyelitis                                                         Simian picornavirus, all types                                                POXVIRUSES                                                                    Alastrim (Variola minor)                                                      Bovine papular stomatitis                                                     Canary pox                                                                    Cotia                                                                         Cowpox                                                                        Embu                                                                          Fibroma                                                                       Fowlpox                                                                       Milker's nodule virus                                                         Monkeypox                                                                     Myxoma                                                                        Rabbit fibroma                                                                Rabbitpox                                                                     Raccoonpox                                                                    Smallpox                                                                      Swine pox                                                                     Tanapox                                                                       Vaccinia                                                                      Yabu tumor poxvirus                                                           REOVIRUSES                                                                    Avian reovirus, all types                                                     Feline reovirus                                                               Reovirus, all types                                                           Turkey enteric reovirus                                                       RETROVIRUSES                                                                  Avian leukosis-sarcoma complex                                                Avian reticuloendotheliosis group                                             Feline leukemia group                                                         Murine leukemia-sarcoma group                                                 Bovine syncytial virus                                                        Caprine arthritis-encephalitis virus                                          Feline syncytia-forming                                                       Human T-cell leukemia virus                                                   Human immunodeficiency virus                                                  Mouse mammary tumor                                                           Simian foamyvirus                                                             Squirrel monkey retrovirus                                                    Syncytium-forming virus of Marmosets                                          Visna virus                                                                   RHABDOVIRUSES                                                                 Aruac                                                                         Bovine paralytic rabies                                                       Chaco                                                                         Chandipura                                                                    Cocal virus                                                                   Hart virus                                                                    Infectious hematopoietic necrosis                                             Jurona                                                                        Kern Canyon                                                                   Klamath                                                                       Kwatta                                                                        Lagos bat                                                                     March                                                                         Mokola                                                                        Mossuril                                                                      Mount Elgon bat                                                               Navorro                                                                       Piry virus                                                                    Rabies                                                                        Sawgrass                                                                      Timbo                                                                         Vesicular stomatitis                                                          ROTAVIRUSES                                                                   Bovine rotavirus                                                              Calf rotavirus                                                                Human rotavirus                                                               Porcine pararotavirus                                                         Porcine rotavirus                                                             Rhesus rotavirus                                                              Simian rotavirus                                                              TOGAVIRUSES                                                                   Alphavirus group                                                              Pestiviruses                                                                  Rubeviruses                                                                   UNCLASSIFIED VIRUSES                                                          Anaplasma marginale                                                           Creutzfeldt-Jakob                                                             Duck hepatitis                                                                Eretmapodites                                                                 Equine infectious anemia virus                                                Frog virus 3                                                                  Golden shine virus                                                            Grunt fin agent                                                               Hepatitis A virus                                                             Hepatitis B virus                                                             Ichampadi                                                                     Infectious bursal disease of chickens                                         Infectious pancreatic necrosis of trout                                       Infectious pancreatic necrosis virus                                          Kuru                                                                          Lymphocystis                                                                  Matucare                                                                      Nodamura virus                                                                Quaranfil                                                                     Tadpole edema virus                                                           Tembe                                                                         Venkatapuram                                                                  Wanowrie                                                                      PLANT VIRUSES                                                                 Agropyron Mosaic                                                              Alfalfa Mosaic                                                                Apple Chlorotic                                                               Apple Mosaic                                                                  Artichoke Latent                                                              Barley Stripe Mosaic                                                          Barley Yellow Dwarf                                                           Bean Common Mosaic                                                            Bean Golden Mosaic                                                            Bean Pod Mottle                                                               Bearded Iris Mosaic                                                           Beet Curly Top                                                                Beet Mosaic                                                                   Beet Western Yellows                                                          Belladonna Mottle                                                             Bidens Mottle                                                                 Broad Bean                                                                    Broccoli Necrotic                                                             Carnation Mottle                                                              Cherry Leaf Rool                                                              Chrysanthemum Aspermy                                                         Citrange Stunt                                                                Cowpea Chlorotic Mottle                                                       Desmodium Yellow Mottle                                                       Elm Mosaic                                                                    Glycine Mottle                                                                Grapevine Fanleaf                                                             Henbane Mosaic                                                                Lettuce Mosaic                                                                Lychnis Ringspot                                                              Maize rough Dwarf                                                             Myrobalan Latent Ringspot                                                     Nasturtium Ringspot                                                           Oat Blue Dwarf                                                                Onion Yellow Dwarf                                                            Pangola Stunt                                                                 Panicum Mosaic                                                                Passionfruit Woodiness                                                        Peanut Stunt                                                                  Plantago Mottle                                                               Poa Semilatent                                                                Pokeweed Mosaic                                                               Prunus Necrotic Ringspot                                                      Raspberry Bushy Dwarf                                                         Scophularia Mottle                                                            Tobacco Mosaic                                                                Tomato Aspermy                                                                Tulip Breaking                                                                Watermelon Mosaic                                                             White Clover Mosaic                                                           Wound Tumor                                                                   ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        MISCELLANEOUS ORGANISMS                                                       ______________________________________                                                   Chlamydia psittaci                                                            Chlamydia trachomatis                                                         Coxiella burneti                                                              Ehrlichia risticii                                                            Rickettsia akari                                                              Rickettsia canada                                                             Rickettsia conori                                                             Rickettsia montana                                                            Rickettsia mooseri                                                            Rickettsia prowazeki                                                          Rickettsia rickettsii                                                         Rickettsia sennetsu                                                           Rickettsia tsutsugamushi                                                      Rochalimaea quintana                                                          Rochalimaea yinsonii                                                          Thai tick typhus                                                              Wolbachia persica                                                  ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        GRAM NEGATIVE BACTERIA                                                        ______________________________________                                        Acetobacter acet   Flavobacterium                                             Acholeplasma laidlawii                                                                           meningosepticum                                            Achromobacter viscosus                                                                           Francisella tularensis                                     Acidiphilium cryptum                                                                             Fusobacterium necrophorum                                  Acinetobacter calcoaceticus                                                                      Gardnerella vaginalis                                      Acinetobacter anatratus                                                                          Haemophilus aegyptius                                      Acinetobacter lwoffii                                                                            Hafnia alvei                                               Actinomyces bovis  Klegsiella oxytoca                                         Actinomyces israelii                                                                             Klebsiella pneumoniae                                      Actinomyces pyogenes                                                                             Legionella cherrii                                         Actinoplanes violaceus                                                                           Legionella feelei                                          Aeromonas hydrophila                                                                             Legionella pneumophila                                     Aeromonas salmonicida                                                                            Leptospira biflexa                                         Agrobacterium tumefaciens                                                                        Moraxella phenylpyruvica                                   Alcaligenes denitrificans                                                                        Morganella morganii                                        Alcaligenes faecalis                                                                             Mycoplasma canis                                           Anaerorhabdus furcosus                                                                           Mycoplasma hyorhinis                                       Aquaspirillum anulus                                                                             Mycoplasma pneumoniae                                      Arachnia propionica                                                                              Neisseria gonorrhoea                                       Arthrobacter ilicis                                                                              Neisseria meningitidis                                     Azotobacter beijerinckii                                                                         Oligella urethralis                                        Bacteroides bivius Pasteurella multocida                                      Bacteroides fragilis                                                                             Proteus mirabilis                                          Bacteroides levii  Proteus vulgaris                                           Bdellovibrio solpii                                                                              Providencia rettgeri                                       Beggiatoa alba     Providencia rustigianii                                    Beijerinckia indica                                                                              Providencia stuartii                                       Bifidobacterium boum                                                                             Pseudomonas aeruginosa                                     Bordetella bronchiseptica                                                                        Pseudomonas avenae                                         Bordetella pertussis                                                                             Pseudomonas cepacia                                        Borrelia burgdorferi                                                                             Pseudomonas pseudomallei                                   Brucella abortus   Pseudomonas putida                                         Campylobacter coli Salmonella choleraesuis                                    Campylobacter jejuni                                                                             Salmonella typhi                                           Campylobacter pylori                                                                             Salmonella typhimurium                                     Chlamydia psittaci Serratia liquefaciens                                      Chlamydia trachomatis                                                                            Serratia marcescens                                        Chromobacterium violaceum                                                                        Shigella boydi                                             Citrobacter freundii                                                                             Shigella dysenteriae                                       Comamonas terrigena                                                                              Shigella flexneri                                          Deleya aesta       Shigella sonnei                                            Deleya venusta     Thiobacillus thiooxidans                                   Dermatophilus congolensis                                                                        Treponema hyodysenteriae                                   Edwardsiella tarda Treponema pallidum                                         Eikenella corrodens                                                                              Ureaplasma gallorale                                       Enterobacter aerogenes                                                                           Veillonella caviae                                         Enterococcus avium Vibrio cholerae                                            Enterococcus faecalis                                                                            Wolinella succinogenes                                     Enterobacter cloacae                                                                             Xanthobacter flavus                                        Erwinia citreus    Xanthomonas campestris                                     Escherichia coli   Yersinia pestis                                            Ewingella americana                                                                              Zymomonas mobilis                                          ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        GRAM POSITIVE BACTERIA                                                        ______________________________________                                        Deinococcus erythromyxa                                                                         Mycobacterium bovis                                         Deinococcus proteolyticus                                                                       Mycobacterium fortuitum                                     Erysipelothrix insidiosa                                                                        Mycobacterium                                               Erysipelothrix rhusiopathiae                                                                    intracellulare                                              Eubacterium aerofaciens                                                                         Mycobacterium leprae                                        Eubacterium angustum                                                                            Mycobacterium tuberculosis                                  Eubacterium combesii                                                                            Norcardia asteroides                                        Eubacterium eligens                                                                             Norcardia brasiliensis                                      Eubacterium fossor                                                                              Paracoccus denitrificans                                    Jonesia denitrificans                                                                           Pediococcus dextrinicus                                     Kurthia gibsonii  Peptostreptococcus                                          Lactobacillus agilis                                                                            asaccharolyticus                                            Lactobacillus brevis                                                                            Peptostreptococcus micros                                   Lactobacillus buchneri                                                                          Phormidium sp                                               Lactobacillus carnis                                                                            Planococcus citreus                                         Lactobacillus casei                                                                             Propionibacterium acnes                                     Lactobacillus divergens                                                                         Propionibacterium                                           Lactobacillus helveticus                                                                        freudenreichii                                              Lactobacillus jensenii                                                                          Rhodococcus equi                                            Lactobacillus kefir                                                                             Rhodococcus erythropolis                                    Lactobacillus xylosis                                                                           Sarcina maxima                                              Lactococcus garviae                                                                             Staphylococcus aureus                                       Lactococcus lactis                                                                              Staphylococcus epidermidis                                  Lactococcus plantarum                                                                           Staphylococcus hominis                                      Leptothrix buccalis                                                                             Staphylococcus warneri                                      Leuconostoc lactis                                                                              Stomatococcus                                               Leuconostoc mesenteroides                                                                       mucilaginosus                                               Leuconostoc oenos Streptobacillus                                             Listeria grayi    moniliformis                                                Listeria innocua  Streptococcus dysgalactiae                                  Listeria monocytogenes                                                                          Streptococcus equi                                          Micrococcus agilis                                                                              Streptococcus equisimilus                                   Micrococcus cryophilus                                                                          Streptococcus faecalis                                      Micrococcus halobius                                                                            Streptococcus pyogenes                                      Micrococcus luteus                                                                              Streptomyces albulus                                        Mycobacterium aurum                                                                             Streptomyces vulgaris                                       Mycobacterium avium                                                           ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        GRAM POSITIVE SPORE FORMING BACTERIA                                          Bacillus            Clostridium                                               ______________________________________                                        acidocaldarius      acetobutylicum                                            alcalophilus        acidiurici                                                alvei               aerotolerans                                              aminoglucosidicus   barkeri                                                   aneurinolyticus     beijerinckii                                              anthracis           bifermentans                                              badius              botulinum                                                 brevis              cadaveris                                                 capitovalis         carnis                                                    cereus              cellulolyticum                                            chitinosporus       chauvoei                                                  circulans           clostridiiforme                                           cirroflagellosus    coccoides                                                 coagulans           collagenovorans                                           epiphytus           cylindrosporum                                            fastidiosus         difficile                                                 filicolonicus       durum                                                     firmus              flavum                                                    freudenreichii      formicoaceticum                                           fructosus           haemolyticum                                              globigii            hastiforme                                                globisporus         histolyticum                                              gordonae            indolis                                                   implexus            kaneboi                                                   insolitus           kluyveri                                                  laevolacticus       lentoputrescens                                           larvae              limosum                                                   laterosporus        lortetii                                                  lentimorbus         perfringens                                               lentus              putrificum                                                licheniformis       septicum                                                  megaterium          sordellii                                                 mycoides            sporogenes                                                pumilus             tetani                                                    schlegelii          tetanomorphum                                             stearothermophilus  thermocellum                                              subtilis            thermolacticum                                            thuringiensis       tyrobutyricum                                             xerothermodurans    villosum                                                  ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        FUNGI                                                                         ______________________________________                                        Absidia blakesleeana                                                                            Entonaema liquescens                                        Achaetomium luteum                                                                              Epidermophyton floccosum                                    Achlya hypogyna   Filobasidiella neoformans                                   Aciculoconidium aculeatum                                                                       Fonsecaea pedrosoi                                          Acladium castellanii                                                                            Fusarium solani                                             Acemoniella lutzi Geotrichum candidum                                         Acrodontium salmoneum                                                                           Gibberella baccata                                          Actinodendron verticillatum                                                                     Gymnosporangium globosum                                    Actinomucor elegans                                                                             Histoplasma capsulatum                                      Acytostelium elipticum                                                                          Kluyveromyces wickerhamii                                   Agaricus abruptibulbus                                                                          Madurella mycetomi                                          Agaricus campestris                                                                             Melampsora medusae                                          Akenomyces costatus                                                                             Microsporum canis                                           Alternaria alternata                                                                            Mucor hiemalis                                              Alternaria citri  Nectriella pironii                                          Armillaria limonea                                                                              Neurospora tetrasperma                                      Arthrobotrys oligospora                                                                         Paecilomyces lilacinus                                      Arthroderma benhamiae                                                                           Penicillium aurantiogriseum                                 Arthroderma gypseum                                                                             Phialophora richardsiae                                     Arthroderma incurvatum                                                                          Phycomyces nitens                                           Articulospora tetracladia                                                                       Pichia membranaefaciens                                     Aspergillus carneus                                                                             Pityrosporium ovale                                         Aspergillus fischeri                                                                            Pseudallescheria boydii                                     Aspergillus fumigatus                                                                           Puccinia graminis                                           Aspergillus niger Pyrenophora trichostoma                                     Aureobasidium mansonii                                                                          Rhizoctonia repens                                          Basidiobolus haptosporus                                                                        Rhizomucor pusillus                                         Blastobotrys aristata                                                                           Rhizopus microsporus                                        Blastomyces dermatitidis                                                                        Rhodotorula rubra                                           Blastoschizomyces capitatus                                                                     Rhynchosporium secalis                                      Botrytis squamosa Saccharomyces cerevisiae                                    Byssochlamys fulva                                                                              Sclerotium rolfsii                                          Candida albicans  Sporothrix schenckii                                        Candida tropicalis                                                                              Sporotrichum thermophile                                    Cephalosporium deformans                                                                        Stemphylium botryosum                                       Ceratocytis ulmi  Torula thermophila                                          Chaetomium globosum                                                                             Torulopsis pintolopesii                                     Chrysosporium pannorum                                                                          Trichoderma polysporum                                      Cladosporium carpophilum                                                                        Trichophyton mentagrophytes                                 Cladosporium resinae                                                                            Trichophyton rubrum                                         Coccidioides immitis                                                                            Ulocladium botrytis                                         Cronartium fusiforme                                                                            Uromyces phaseoli                                           Cryptococcus neoformans                                                                         Verticillium nigrescens                                     Curvularia prasadii                                                                             Xylohypha bantiana                                          Dictyostelium discoideum                                                                        Yarrowia lipolytica                                                           Zygosaccharomyces bailii                                    ______________________________________                                    

                  TABLE VII                                                       ______________________________________                                        PROTISTS - ALGAE/PROTOZOA                                                     ______________________________________                                        Acanthamoeba astronyxis                                                                         Leishmania hertigi                                          A. castellanii    Leishmania mexicana                                         A. culbertsoni    Leishmania tropica                                          A. hatchetti      Leptomonas pyrrhocoris                                      A. lenticulata    Lingulamoeba leei                                           A. polyphaga      Lohomonas piriformis                                        A. royreba        Monocercomonas colubrorum                                   Babesia microti   Muriella aurantiaca                                         Botrydium cystosum                                                                              Naegleria australiensis                                     Cephaleuros virescens                                                                           Naegleria fowleri                                           Chlamydomonas dorsoventralis                                                                    Naegleria gruberi                                           Chlorella protothecoides                                                                        Naegleria jadini                                            Chlorella saccharophilia                                                                        Nosema necatrix                                             Chlorella sorokiniana                                                                           Ochromonas malhamensis                                      Chlorella variegata                                                                             Paramecium primaurelia                                      Chlorella xanthella                                                                             Paramecium                                                  Chlorella zopfingiensis                                                                         multimicronucleatum                                         Chlorogonium elongatum                                                                          Pentatrichoimonas hominis                                   Crithidia fasciculata                                                                           Plasmodium brasilianum                                      Dientamoeba fragilis                                                                            Plasmodium coatneyi                                         Dunaliella tertiolecta                                                                          Plasmodium cynomolgi                                        Entamoeba coli    Plasmodium falciparum                                       Entamoeba gingivalis                                                                            Plasmodium vivax                                            Entamoeba histolytica                                                                           Prototheca wickerhamii                                      Euglena gracilis  Tetracystis disociata                                       Giardia intestinalis                                                                            Tetrahymena borealis                                        Giardia lamblia   Tetrahymena thermophila                                     Haematococcus lacustris                                                                         Trichomonas gallinae                                        Hartmannella limax                                                                              Trichomonas vaginalis                                       Herpetomonas mariadeanei                                                                        Tritrichomonas foetus                                       Leishmania braziliensis                                                                         Trypanosoma brucei                                          Leishmania donovani                                                                             Trypanosoma cruzi                                           ______________________________________                                    

We claim:
 1. A biocidal, aqueous, composition for killing bacteria,spores, fungi, and viruses on nonabsorbent surface comprising:a) twoquaternary ammonium compounds, each in the amount of from about 0.05 to3 percent by weight, one of said two quaternary ammonium compounds is aheterocyclic quaternary ammonium compound, and the other of saidquaternary ammonium compounds is an aliphatic quaternary ammoniumcompound having an aromatic and an alkyl moiety or having a long chainaliphatic and a lower alkyl moiety; b) one heterocyclic dialdehydecontaining up to 6 carbon atoms in the amount of from about 0.5 to about7 percent by weight; and c) at least one aliphatic hydroxyl compoundhaving from 1 to 8 carbon atoms in the amount from 0.1 to about 3percent by weight; all weight percents being in the final use dilution.2. The biocidal composition of claim 1, wherein the weight percent ofthe heterocyclic dialdehyde in the final use dilution is in the amountof from about 2.6 to about 5 weight percent.
 3. The biocidal compositionof claim 1, further comprising a cheating agent in the amount of zero toabout 0.025 weight percent of the final use dilution.
 4. The biocidalcomposition of claim 3, wherein the cheating agent is tetrasodiumethylenediamine tetraacetate.
 5. The biocidal composition of claim 1,wherein the pH ranges from about 4 to about
 9. 6. The biocidalcomposition of claim 1, wherein the dialdehyde is furan-2,5-dialdehydecomprising from 2.6 to 3.2 weight percent of the final use dilution. 7.The biocidal composition of claim 1, wherein the heterocyclic quaternaryammonium compound is n-hexylpyridinium halide.
 8. The biocidalcomposition of claim 1, wherein the aliphatic quaternary ammoniumcompound contains an aromatic moiety which is benzylalkyl.
 9. Thebiocidal composition of claim 1, wherein the aliphatic quaternaryammonium compound contains a long chain aliphatic moiety which iscetyldimethylethyl.
 10. The biocidal composition of claim 1, wherein thealiphatic hydroxy compound is selected from the group consisting ofisopropyl alcohol, propylene glycol, and their mixtures.
 11. Thebiocidal composition of claim 1, further comprising a soluble,inorganic, nitrite salt.
 12. The biocidal composition of claim 1,wherein all the all the quaternary ammonium compounds are halide salts.13. A method for sterilizing a nonabsorbent surface comprising the stepsof contacting said surface with an effective sterilizing amount of anaqueous composition comprising:a) two quaternary ammonium compounds,each in the amount of from about 0.05 to 3 percent by weight, one ofsaid two quaternary ammonium compounds is a heterocyclic quaternaryammonium compound, and the other of said quaternary ammonium compoundsis an aliphatic quaternary ammonium compound having an aromatic and analkyl moiety or having a long chain aliphatic and a lower alkyl moiety;b) one heterocyclic dialdehyde containing up to 6 carbon atoms in theamount of from about 0.5 to about 7 percent by weight; and c) at leastone aliphatic hydroxyl compound having from one to eight carbon atoms inthe amount from about 0.1 to about 3 percent by weight; all weightpercents being in the final use dilution; and killing on said surfacebacteria, spores, fungi, and viruses.